JP2020507649A - Thermoplastic polyurethane - Google Patents

Abstract

The present invention relates to compounds comprising at least one polyisocyanate composition, at least one chain extender of general formula (I) (KV1) and at least two isocyanate-reactive groups having a molecular weight of <500 g / mol. A further chain extender (KV2) selected from the group, as well as a thermoplastic polyurethane obtainable or obtainable by reaction of at least one polyol composition. The invention furthermore relates to a process for the production of such thermoplastic polyurethanes and to the thermoplastic polyurethanes according to the invention or to the thermoplastics obtainable or obtainable by the process according to the invention for producing extruded products, films and moldings. It relates to the use of polyurethane.

Description

  The invention relates to at least one polyisocyanate composition, at least one chain extender of general formula (I) (KV1) and a compound having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol. A further chain extender (KV2) selected from the group, as well as a thermoplastic polyurethane obtainable or obtainable by reaction of at least one polyol composition. The invention furthermore relates to a process for the production of such thermoplastic polyurethanes and the thermoplastic polyurethanes according to the invention or thermoplastics obtainable or obtainable by the process according to the invention for producing extruded products, films and moldings. It relates to the use of polyurethane.

  Thermoplastic polyurethanes for various applications are known in principle from the prior art. By changing the feedstock, it is possible to obtain profiles with different properties.

  For example, WO 2006/082183 A1 is a process for the continuous production of thermoplastically processable polyurethane elastomers, comprising a polyisocyanate, a compound having a Zerowittinoff active hydrogen atom with an average molecular weight of 450 g / mol to 5000 g / mol. , Chain extenders and those which react further auxiliary and additive materials. A particular profile of a property is achieved by a particular process.

  EP 0 922 552 A1 is also a process for continuously producing granules from thermoplastic polyurethane elastomers, comprising an organic diisocyanate, a difunctional polyhydroxyl compound having a molecular weight of 500 to 8000 and a bifunctional compound having a molecular weight of 60 to 400. Disclosed are those in which a granulate is first produced by reacting a sex chain extender in the presence of a catalyst and auxiliaries and / or additives. Uses for producing extrudates, injection moldings or calendarings, in particular cable coatings, hoses and / or films, are likewise disclosed.

  WO 98/56845 A1 discloses thermoplastic polymers obtained by the reaction of polyisocyanates, glycols as chain extenders and polyether polyols. Various isocyanates, chain extenders and polyols have been disclosed.

  Depending on the application, the properties of the thermoplastic polyurethane can be varied depending on the type of input and the proportions used. For example, stability can be affected by variations in the polyol component. Stability can also be affected by processing, eg, heat treatment. The change of the hard phase also makes it possible to influence the mechanical properties and the extrusion quality.

  However, the mechanical properties of thermoplastic polyurethanes are often insufficient for individual applications.

  Therefore, proceeding from the prior art, it is an object of the present invention to provide an improved material that exhibits good mechanical properties.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）
−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択され、
Ａ及びＱは、同時にＣＨ_２ではない）
（ｉｉｉ）少なくとも１種のポリオール組成物、
の反応によって得ることが可能な又は得られる熱可塑性ポリウレタンであって、
＜５００ｇ／ｍｏｌの分子量を有する少なくとも２個のイソシアネート反応性基を有する化合物からなる群から選択される少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、熱可塑性ポリウレタンによって達成される。 According to the invention, this object is achieved at least by components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3)
-OH, selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time)
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
This is achieved by a thermoplastic polyurethane in which at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

  Surprisingly, it has been found that the inventive combination of components (i) to (iii) makes it possible to obtain thermoplastic polyurethanes which exhibit not only good mechanical properties but also improved extrusion quality. Was. The thermoplastic polyurethanes of the present invention exhibit particularly improved compression set. The optical properties of the resulting extruded product are also significantly improved, for example, through smoother surfaces.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択される）。基Ｒ１及びＲ２は、任意にＯＨ官能化され得るアルキル基である。Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、ｎは、０、１、２、３、４、５又は６であり、Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される。本発明によれば、Ａ及びＱは、同時にＣＨ_２ではない。本発明によれば、＜５００ｇ／ｍｏｌの分子量を有する少なくとも２個のイソシアネート反応性基を有する化合物からなる群から選択される少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる。 According to the present invention, at least components (i) to (iii) are reacted. What is used according to the invention as a chain extender is at least one chain extender (KV1) of the general formula (I),

(In the formula, A, O, N (R3), S, is selected from CH _2, Q is, O, N (R3), S, is selected from CH _2). The groups R1 and R2 are alkyl groups which can be optionally OH-functionalized. R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH, R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) - CH ₂ —OH, CH ₂ —CH (CH ₃ ) —OH, OH, n is 0, 1, 2, 3, 4, 5, or 6, and R ₃ is CH ₃ , CH ₂ —CH _{3 is} selected. According to the present invention, A and Q are not simultaneously CH _2. According to the invention, at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

  Suitable compounds which can be employed as chain extenders (KV1) of the formula (I) are known per se to the person skilled in the art. For example, one suitable chain extender (KV1) is hydroquinone bis (2-hydroxyethyl) ether.

  Therefore, in a further embodiment, the present invention also relates to a thermoplastic polyurethane as described above, wherein the chain extender (KV1) of general formula (I) is hydroquinone bis (2-hydroxyethyl) ether.

  Based on the total amount of chain extender, the further chain extender (KV2) typically has an amount of 1% to 50%, preferably 1% to 30%, more preferably 1% to 25%. It is employed in an amount, more preferably in an amount of 5% to 20%, particularly preferably in an amount of 5% to 10%.

  Compounds having at least two isocyanate-reactive groups are employed as further chain extenders (KV2). The isocyanate-reactive groups can in particular be NH, OH or else SH groups. Suitable compounds are known per se to the person skilled in the art. For example, diamines or other diols are suitable. Thus, in a further embodiment, the present invention also relates to a thermoplastic polyurethane as described above, wherein the at least one further chain extender is selected from aliphatic and aromatic diols having a molecular weight of <500 g / mol.

  In one embodiment of the invention, a diol having a molecular weight of <350 g / mol is employed as a further chain extender (KV2). In a further embodiment, the present invention also relates to a thermoplastic polyurethane as described above, wherein said at least one further chain extender (KV2) is selected from aliphatic and aromatic diols having a molecular weight of <350 g / mol.

  Aliphatic, araliphatic, aromatic and / or alicyclic diols having a molecular weight of from 50 g / mol to 220 g / mol can be more preferably employed. Alkanediols having 2 to 10 carbon atoms in the alkylene group, in particular di-, tri-, tetra-, penta-, hexa-, hepta, octa, nona and / or decaalkylene glycols, are preferred. Particularly preferred for the present invention are 1,2-ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

  Also suitable as chain extenders (KV2) in the context of the present invention are 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethyl-1,3 -A branched compound such as pentanediol, pinacol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanediol or N-phenyldiethanolamine. Similarly, compounds having OH and NH groups, such as 4-aminobutanol, are also suitable.

  According to the invention, it is also possible to employ further chain extenders. Third and / or fourth chain extenders of this type are typically employed in amounts less than 10% based on the amount of chain extender employed.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）。 In a further embodiment, it is possible in the context of the present invention to employ as further chain extender (KV2) a compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from _{CH 3, CH 2 -CH 3)} .

  Comments: Since this combination is already included in the general formula (as in the case with other R2), the following has been deleted.

  It is preferred when the compound of the general formula (II) is resorcinol bis (2-hydroxyethyl) ether.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）。 Thus, in a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein at least one further chain extender (KV2) is a compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from _{CH 3, CH 2 -CH 3)} .

  In a preferred embodiment of the present invention, hydroquinone bis (2-hydroxyethyl) ether is employed as the chain extender of formula (I) (KV1) and resorcinol bis (2-hydroxyethyl) ether is used as the further chain extender (KV2). Adopted.

  In the context of the present invention, the amount of chain extender employed and the polyol composition can be varied within wide limits. For example, component (iii) and component (ii) are used at a molar ratio of (iii) to (ii) of 1 to 0.7, 1 to 2.7 and 1 to 7.3.

  Comment: Information on HS / WS is as follows.

According to the present invention, the polyol composition comprises at least one polyol. Polyols are known in principle to the person skilled in the art and are described, for example, in "Kunststoffhandbuch", volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Particularly preferred polyols are polyesterols or polyetherols. Polycarbonate can be employed as well. Copolymers can also be used in the context of the present invention. The number average molecular weight of the polyol used according to the invention, ^{preferably, 0.5 × 10 3 g / mol~8} × 10 3 g / mol, preferably ^{0.6 × 10 3 g / mol~5 ×} 10 3 g / mol, in particular ^{0.8 × 10 3 g / mol~3 ×} 10 3 g / mol.

  In addition to polyetherols, polyesters, block copolymers, and hybrid polyols such as poly (ester / amide) are also suitable for the present invention. According to the invention, preferred polyetherols are polyethylene glycol, polypropylene glycol, polyadipate, polycarbonate, polycarbonate diol and polycaprolactone.

  In another embodiment, the present invention also relates to the aforementioned thermoplastic polyurethane, wherein the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, polycaprolactone and polycarbonate.

  Suitable polyols are, for example, polyetherols such as polytrimethylene oxide or polytetramethylene oxide.

  Suitable block copolymers are, for example, those with ether and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks, and also polyethers with polycaprolactone end blocks. According to the invention, preferred polyetherols are polyethylene glycol and polypropylene glycol. Polycaprolactone is also preferred.

  In a particularly preferred embodiment, the polyol employed has a number average molecular weight Mn in the range from 500 g / mol to 4000 g / mol, preferably from 800 g / mol to 3000 g / mol.

  Therefore, in a further embodiment, the present invention relates to the above thermoplastic polyurethane, wherein at least one polyol present in the polyol composition has a number average molecular weight Mn in the range from 500 g / mol to 4000 g / mol. About things.

  Mixtures of different polyols can also be employed according to the present invention. It is preferred that the polyol / polyol composition employed has an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, especially 2. It is preferred that the polyol used in the present invention has only primary hydroxyl groups.

  In one embodiment of the invention, the production of the thermoplastic polyurethane employs at least one polyol composition comprising at least polytetrahydrofuran as component (iii). According to the invention, the polyol composition may comprise not only polytetrahydrofuran but also further polyols.

  Further polyols suitable for the present invention are, for example, not only polyethers, but also polyesters, block copolymers and also hybrid polyols such as, for example, poly (ester / amide). Suitable block copolymers are, for example, those with ether and ester blocks, for example polycaprolactone with polyethylene oxide or polypropylene oxide end blocks, and also polyethers with polycaprolactone end blocks. According to the invention, preferred polyetherols are polyethylene glycol and polypropylene glycol. Polycaprolactone is also preferred as a further polyol.

  Thus, in a further embodiment, the present invention relates to the above thermoplastic polyurethane, wherein the polyol composition comprises at least one polytetrahydrofuran and further polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and polycaprolactone. And at least one further polyol selected from the group consisting of:

  In a particularly preferred embodiment, the polytetrahydrofuran has a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol, more preferably in the range from 550 g / mol to 2500 g / mol, particularly preferably in the range from 650 g / mol to 2000 g / mol. Having.

  In the context of the present invention, the composition of the polyol composition can be varied within wide limits. For example, the content of the first polyol, preferably polytetrahydrofuran, is in the range of 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.

  According to the present invention, the polyol composition may also include a solvent. Suitable solvents are known per se to the person skilled in the art.

  When polytetrahydrofuran is used, the number average molecular weight Mn of the polytetrahydrofuran is preferably in the range from 500 to 5000 g / mol. The number average molecular weight Mn of polytetrahydrofuran is more preferably in the range of 500 to 1400 g / mol.

  In a further embodiment, the present invention also relates to a thermoplastic polyurethane as described above, wherein said polyol composition is selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol. Related to things containing.

  Further, according to the present invention, a mixture of different polytetrahydrofurans, that is, a mixture of polytetrahydrofurans having different molecular weights can be employed.

  Therefore, in a further embodiment, the present invention relates to the above thermoplastic polyurethane, wherein the polyol composition is selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range from 1501 g / mol to 3000 g / mol. The present invention relates to a composition containing the polyol (P1) and a polyol (P2) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol.

  A polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol in an amount ranging from 5% to 30% and an amount ranging from 2% to 50%; It is customary to employ a mixture comprising polytetrahydrofuran having a number average molecular weight Mn in the range from 500 g / mol to 1500 g / mol.

  According to the present invention, the production of thermoplastic polyurethane employs a polyisocyanate composition.

  Preferred polyisocyanates in the context of the present invention are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

  Also, in the context of the present invention, as the isocyanate component, a pre-reacted product in which a part of the OH component has reacted with the isocyanate in the preceding reaction step can be employed. The resulting product is reacted with the remaining OH component in the next step, which is the actual polymer reaction, thereby forming a thermoplastic polyurethane.

  The aliphatic diisocyanates employed are the customary aliphatic and / or cycloaliphatic diisocyanates such as, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentane Methylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene, 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1, 6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI) With cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate, methylenedicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI) is there.

  Preferred aliphatic polyisocyanates are hexamethylene 1,6-diisocyanate (HDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4 ′-, 2,4′- and / or Or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).

  Preferred aliphatic polyisocyanates are hexamethylene 1,6-diisocyanate (HDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4′-, 2,4′- and / or Or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI); particularly preferred are 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI) and 1-isocyanato- 3,3,5-trimethyl-5-isocyanatomethylcyclohexane or a mixture thereof.

  Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,2′-, 2,4′- and And / or 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (TODI), p-phenylenediisocyanate (PDI), 4,4'-diphenylethane diisocyanate ( EDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate.

  In a preferred embodiment of the present invention, only one isocyanate is used. In particular, it is preferred that a mixture containing 4,4'-MDI and further isocyanate is not employed.

  Preferred examples of polyfunctional isocyanates are triisocyanates, for example triphenylmethane-4,4 ', 4 "-triisocyanate, and also the isocyanurates of the above diisocyanates, and the partial reaction of diisocyanates and water. Oligomers, such as biurets of the above-mentioned diisocyanates, as well as oligomers obtainable by the specific reaction of half-blocked diisocyanates with polyols having on average more than 2, preferably more than 3, or more hydroxyl groups. is there.

  According to the present invention, the polyisocyanate composition may also include one or more solvents. Suitable solvents are known to those skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.

  Also, in the context of the present invention, crosslinkers, such as the above-mentioned polyfunctional polyisocyanates or polyols, or other polyfunctional molecules having a plurality of isocyanate-reactive functional groups can be employed. Similarly, in the context of the present invention, it is possible to achieve crosslinking of the product via an excess of employed isocyanate groups over hydroxyl groups.

  According to the invention, the components (i) to (iii) have a molar ratio of the total functionality of the polyol composition and the chain extender employed to the total functionality of the isocyanate composition employed of 1: It is adopted so as to be in the range of 0.8 to 1: 1.3. This ratio preferably ranges from 1: 0.9 to 1: 1.2, more preferably ranges from 1: 0.965 to 1: 1.11, and more preferably ranges from 1: 0.97 to 1: 1. 11, more preferably in the range of 1: 0.97 to 1: 1.05, particularly preferably in the range of 1: 0.98 to 1: 1.03.

  In a further embodiment, the present invention relates to the above thermoplastic polyurethane, wherein the molar ratio of the total functionality of the polyol composition and the chain extender employed to the total functionality of the isocyanate composition employed is 1%. : 0.8 to 1: 1.3.

  A further parameter considered in the reaction of components (i) to (iii) is the isocyanate index. The index is defined by the ratio of the isocyanate groups of component (i) employed in the reaction to all isocyanate-reactive groups, ie, in particular, the groups of components (ii) and (iii). At an index of 1000, there is one active hydrogen atom for each isocyanate group of component (i). When the index exceeds 1000, there are more isocyanate groups than isocyanate-reactive groups. The index in the reaction of the components (i) to (iii) is preferably 965 to 1110, for example, 970 to 1110, more preferably 970 to 1050, and particularly preferably 980 to 1030.

  In a further embodiment, the present invention relates to the above-mentioned thermoplastic polyurethane, wherein the index of reaction ranges from 965 to 1100.

  According to the invention, further additives, such as catalysts or auxiliaries and additives, can be added during the reaction of components (i) to (iii). Additives and auxiliaries are known per se to the person skilled in the art. Combinations of two or more additives may also be employed in accordance with the present invention.

  In the context of the present invention, the term additive shall mean, in particular, catalysts, auxiliaries and additives, in particular stabilizers, nucleating agents, release agents, demolding agents, fillers, flame retardants or crosslinkers. I want to be understood.

  Suitable additives are, for example, stabilizers, nucleating agents, fillers, for example silicates, or crosslinkers, for example polyfunctional aluminosilicates.

  Thus, in a further embodiment, the present invention relates to a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane comprises at least one additive.

  Examples of auxiliaries and additives are surfactants, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants and demolding auxiliaries, dyes and pigments, for example hydrolysis, light, heat or discoloration Stabilizers, inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliaries and additives can be found, for example, in Kunststoffhandbuch, volume VII (edited by Viewweg and Hoechtlen), Carl Hanser Verlag, Munich 1966 (pp. 103-113).

  Likewise suitable catalysts are known in principle from the prior art. Suitable catalysts are, for example, organometallic compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and organoiron, for example organotin compounds, preferably tin dialkyls such as dimethyltin or diethyltin. Compounds or tin organotin compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds, or iron compounds, preferably iron (MI) acetylacetate Or metal salts of carboxylic acids, such as tin (II) isooctoate, tin dioctoate, titanate ester or bismuth (III) neodecanoate.

  In a preferred embodiment, the catalyst is selected from a tin compound and a bismuth compound, more preferably a tin alkyl compound or a bismuth alkyl compound. Tin (II) isooctoate and bismuth neodecanoate are particularly preferred.

  The catalyst is typically used in an amount of 0 to 2000 ppm, preferably 1 ppm to 1000 ppm, more preferably 2 ppm to 500 ppm, most preferably 5 ppm to 300 ppm.

  The properties of the thermoplastic polyurethanes according to the invention can be varied within wide limits depending on the application.

  The hard segment portion of the thermoplastic polyurethanes according to the invention is typically in the range from 5% to 70%, especially in the range from 10% to 50%, preferably in the range from 15% to 45%. In the context of the present invention, the hard segment portion is determined according to the formula disclosed in WO2007 / 118827A1.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択され、
Ａ及びＱは、同時にＣＨ_２ではない）
（ｉｉｉ）少なくとも１種のポリオール組成物、
の反応を含む可塑性ポリウレタンの製造方法であって、
＜５００ｇ／ｍｏｌの分子量を有する少なくとも２個のイソシアネート反応性基を有する化合物からなる群から選択される少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、方法に関する。 In yet another aspect, the present invention also provides at least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time)
(Iii) at least one polyol composition;
A process for producing a flexible polyurethane comprising the reaction of
A process wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

  With regard to preferred embodiments of the method, suitable dosing materials or mixing ratios, reference is made to the corresponding statements made above.

  The reactions (i) to (iii) can in principle be carried out under known reaction conditions. The reaction can be carried out discontinuously or continuously, for example in a belt process or a reactive extrusion process. Suitable methods are described, for example, in EP 0 922 552 A1 or WO 2006/082183 A1.

  In a preferred embodiment, the reaction of components (i)-(iii) is performed at a temperature above room temperature.

  According to the present invention, heating can be performed in any suitable manner known to those skilled in the art. It is also preferred that the charge be heated before addition, for example using a heatable metering unit.

  For example, in a reaction using a reactive extrusion method, the reaction is controlled such that the zone temperature is in the range 170 ° C to 245 ° C, preferably in the range 180 ° C to 235 ° C, more preferably in the range 190 ° C to 230 ° C. Is done.

  Therefore, in a further embodiment, the present invention is a method for producing a thermoplastic polyurethane as described above, wherein the reaction is carried out using a reactive extrusion method, wherein the zone temperature is in the range 170 ° C to 245 ° C. About something.

  According to the invention, the method may also comprise further steps, for example a pre-treatment of the components or a post-treatment of the obtained thermoplastic polyurethane. Therefore, in a further embodiment, the present invention relates to a method for producing a thermoplastic polyurethane as described above, wherein the thermoplastic polyurethane obtained is heat-treated after the reaction.

  The thermoplastic polyurethane according to the invention / polyurethane obtained or obtainable by the method according to the invention can be used in various ways. The thermoplastic polyurethane according to the present invention is particularly suitable for forming molded articles and films. Possible applications are, for example, seals, seal rings, gaskets, sealing washers, sealants, sealing compositions, sealants or outer soles of shoes. Further applications are, for example, hoses, conveyor belts, films, packaging materials, cables, floor applications, shock absorbers and sound absorbers, especially for air applications.

  In a further aspect, the invention is also obtained by a thermoplastic polyurethane as described above or a method according to the invention for producing extruded products, films and moldings, in particular for producing cable coatings, hoses and seals or It relates to the use of the thermoplastic polyurethanes obtainable.

  In a further embodiment, the present invention also relates to the use of a thermoplastic polyurethane as described above or obtained or obtainable by a process according to the invention for producing extruded products, films and molded articles. Extruded products, films or foils which are reinforced by fillers.

  Surprisingly, it has been found that the thermoplastic polyurethanes according to the invention or obtained by the method according to the invention are well suited for the production of foamed materials. The thermoplastic polyurethanes according to the invention can be processed into foamed materials in a manner known per se. Additives such as blowing agents, cell regulators, surfactants, nucleating agents, fillers, hollow microspheres and / or release agents are optionally used. Suitable methods and additives are disclosed, for example, in WO2014 / 198779A1, WO2007 / 082838A1 or WO94 / 20568A1.

  Thus, in a further aspect, the invention also relates to the use of a thermoplastic polyurethane as described above or a thermoplastic polyurethane obtained or obtainable by a method according to the invention, for producing foamed films, foamed moldings or foamed particles. And a particle foam obtained therefrom.

  In a further embodiment, the invention also relates to the use of a thermoplastic polyurethane as described above or a thermoplastic polyurethane obtained or obtainable by a method according to the invention for producing foamed films, foamed moldings or foamed particles. , And particle foams obtained therefrom, wherein the foamed film, the foamed molding or the foamed particles and the particle foams obtainable therefrom are reinforced with fillers.

  In a preferred embodiment, the chain extender mixture is selected such that the TPU has a softening point below 190 ° C., preferably below 160 ° C., very preferably below 150 ° C.

  The softening temperature is a 2 mm injection-molded sheet heat-treated at a temperature of 100 ° C. for 20 hours, a frequency of 1 Hz and a heating rate of 20 K / min (measured from −80 ° C. to 200 ° C.) according to DMA (DIN EN ISO 6721-1: 2011). Measurement).

  Further embodiments of the invention are evident from the claims and the examples. The features of the subject / method / application according to the invention enumerated above and described below can be used not only in the combinations specified in each case, but also in other combinations without departing from the scope of the invention It will be understood that Thus, for example, a combination of a preferred feature with a particularly preferred feature, or a combination of features that are not further characterized, such as a particularly preferred feature, are implicitly included, even if the combination is not explicitly mentioned. You.

  Exemplary embodiments of the invention are described below, but are not intended to limit the invention. In particular, the invention also includes embodiments arising from the dependent references, and hence from the combinations specified below.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択され、
Ａ及びＱは、同時にＣＨ_２ではない）、
（ｉｉｉ）少なくとも１種のポリオール組成物、
の反応によって得ることが可能であるか又は得られる熱可塑性ポリウレタンであって、
＜５００ｇ／ｍｏｌの分子量を有する少なくとも２個のイソシアネート反応性基を有する化合物からなる群から選択される少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、熱可塑性ポリウレタン。 1. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time),
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
A thermoplastic polyurethane, wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

  2. The thermoplastic polyurethane of embodiment 1, wherein the chain extender (KV2) is selected from the group consisting of aliphatic and aromatic diols having a molecular weight of <500 g / mol.

  3. The thermoplastic polyurethane according to embodiment 1 or 2, wherein the chain extender (KV1) of the general formula (I) is hydroquinone bis (2-hydroxyethyl) ether.

  4. The thermoplastic polyurethane according to any of embodiments 1 to 3, wherein said at least one further chain extender (KV2) is selected from aliphatic and aromatic diols having a molecular weight of <350 g / mol.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である、実施形態１〜３のいずれかに記載の熱可塑性ポリウレタン。 5. The at least one further chain extender (KV2) is a compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
The thermoplastic polyurethane according to any one of embodiments 1 to 3, wherein

  6. The thermoplastic polyurethane according to any of embodiments 1 to 5, wherein the polyol composition comprises a polyol selected from the group consisting of polyetherol, polyesterol, polycaprolactone polyol and polycarbonate polyol.

  7. The thermoplastic polyurethane according to any of embodiments 1 to 6, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol.

  8. The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. The thermoplastic polyurethane according to any of embodiments 1 to 7, comprising a polyol (P2) selected from the group consisting of polytetrahydrofuran having

  9. The thermoplastic according to any of embodiments 1 to 8, wherein the polyisocyanate composition comprises an isocyanate selected from the group consisting of TODI, NDI, PDI, 4,4'-MDI and 2,4'-MDI. Polyurethane.

  10. The thermoplastic polyurethane of any of embodiments 1-9, wherein the polyisocyanate composition comprises a mixture of 4,4'-MDI and 2,4'-MDI.

11. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
A thermoplastic polyurethane, wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、熱可塑性ポリウレタン。 12. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
Compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
A thermoplastic polyurethane, wherein at least one further chain extender (KV2) is used.

13. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
At least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol,
The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. A thermoplastic polyurethane comprising a polyol (P2) selected from the group consisting of polytetrahydrofuran having the formula:

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられ、
前記ポリオール組成物が、１５０１ｇ／ｍｏｌ〜３０００ｇ／ｍｏｌの範囲の数平均分子量Ｍｎを有するポリテトラヒドロフランからなる群から選択されるポリオール（Ｐ１）及び５００ｇ／ｍｏｌ〜１５００ｇ／ｍｏｌの範囲の数平均分子量Ｍｎを有するポリテトラヒドロフランからなる群から選択されるポリオール（Ｐ２）を含む、熱可塑性ポリウレタン。 14． At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
Compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
At least one further chain extender (KV2) is used,
The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. A thermoplastic polyurethane comprising a polyol (P2) selected from the group consisting of polytetrahydrofuran having the formula:

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、１、２、３、４、５、６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択され、
Ａ及びＱは、同時にＣＨ_２ではない）、
（ｉｉｉ）少なくとも１種のポリオール組成物、
の反応を含む、熱可塑性ポリウレタンを製造するための方法であって、
＜５００ｇ／ｍｏｌの分子量を有する少なくとも２個のイソシアネート反応性基を有する化合物からなる群から選択される少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、方法。 15. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 1, 2, 3, 4, 5, 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time),
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane, comprising the reaction of
A process wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

  16. Embodiment 16. The method of embodiment 15, wherein the chain extender (KV2) is selected from the group consisting of aliphatic and aromatic diols having a molecular weight of <500 g / mol.

  17． Embodiment 17. The method according to embodiment 15 or 16, wherein the chain extender (KV1) of general formula (I) is hydroquinone bis (2-hydroxyethyl) ether.

  18. Embodiment 18. The method according to any of embodiments 15 to 17, wherein said at least one further chain extender (KV2) is selected from aliphatic and aromatic diols having a molecular weight of <350 g / mol.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である、実施形態１５〜１８のいずれかに記載の方法。 19. The at least one further chain extender (KV2) is a compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
The method according to any of embodiments 15-18, wherein

  20. Embodiment 20. The method of any of embodiments 15 to 19, wherein the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, polycaprolactone polyols and polycarbonate polyols.

  21. 21. The method according to any of embodiments 15-20, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol.

  22. The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. 22. The method according to any of embodiments 15-21, comprising a polyol (P2) selected from the group consisting of polytetrahydrofuran having

  23. 23. The method according to any of embodiments 15-22, wherein the polyisocyanate composition comprises an isocyanate selected from the group consisting of TODI, NDI, PDI, 4,4'-MDI, and 2,4'-MDI.

  24. The method of any of embodiments 15-23, wherein the polyisocyanate composition comprises a mixture of 4,4'-MDI and 2,4'-MDI.

25. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane, comprising the reaction of
A process wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられる、方法。 26. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane, comprising the reaction of
Compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
Wherein at least one further chain extender (KV2) is used.

27. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane, comprising the reaction of
At least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol,
The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. A polyol (P2) selected from the group consisting of polytetrahydrofurans having the formula:

（式中、Ａは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｑは、Ｏ、Ｎ（Ｒ３）、Ｓ、ＣＨ_２から選択され、
Ｒ１は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＯＨから選択され、
Ｒ２は、ＣＨ_２−（ＣＨ_２）_ｎ−ＯＨ、ＣＨ（ＣＨ_３）−ＣＨ_２−ＯＨ、ＣＨ_２−ＣＨ（ＣＨ_３）−ＯＨ、ＯＨから選択され、
ｎは、０、１、２、３、４、５又は６であり、
Ｒ３は、ＣＨ_３、ＣＨ_２−ＣＨ_３から選択される）
である少なくとも１種のさらなる鎖延長剤（ＫＶ２）が用いられ、
前記ポリオール組成物が、１５０１ｇ／ｍｏｌ〜３０００ｇ／ｍｏｌの範囲の数平均分子量Ｍｎを有するポリテトラヒドロフランからなる群から選択されるポリオール（Ｐ１）及び５００ｇ／ｍｏｌ〜１５００ｇ／ｍｏｌの範囲の数平均分子量Ｍｎを有するポリテトラヒドロフランからなる群から選択されるポリオール（Ｐ２）を含む、方法。 28. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) hydroquinone bis (2-hydroxyethyl) ether as at least a chain extender (KV1),
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane, comprising the reaction of
Compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
At least one further chain extender (KV2) is used,
The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. A polyol (P2) selected from the group consisting of polytetrahydrofurans having the formula:

  29. A thermoplastic polyurethane according to any of embodiments 1 to 14 or any of embodiments 15 to 28 for producing extruded products, films and moldings, in particular for producing cable coatings, hoses and seals. Use of a thermoplastic polyurethane obtainable or obtainable by the described method.

  30. The use according to embodiment 29, wherein the extruded product, film or foil is reinforced with a filler.

  31. A thermoplastic polyurethane according to any of embodiments 1 to 14 or any of embodiments 15 to 28 for producing foamed films, foamed moldings or foamed particles and particle foams obtainable therefrom. Use of a thermoplastic polyurethane obtainable or obtainable by the described method.

  32. The use according to embodiment 31, wherein the foam film, foam molding or foam particles and the particle foam obtainable therefrom are reinforced with a filler.

FIG. 1 shows a hose made of thermoplastic polyurethane, which consists of PTHF1000 and a specific hard phase and has a Shore hardness of 98A. The material was produced on a pilot reaction extruder.

  FIGS. 1 (a) and 1 (b) show a hose made from a thermoplastic polyurethane containing a HQEE-MDI hard phase.

  FIGS. 1 (c) and 1 (d) show hoses made from thermoplastic polyurethane containing TPU with HQEE / HER-MDI hard phase.

  The following examples are intended to illustrate the invention but are not intended to limit the subject matter of the invention in any way.

1. The following ingredients were used:
PTHF1000: polytetramethylene oxide (PTHF) Mw 1000 g / mol
PTHF650: polytetramethylene oxide (PTHF) Mw 650 g / mol
PTHF2000: polytetramethylene oxide (PTHF) Mw 2000 g / mol
HQEE: hydroquinone bis (2-hydroxyethyl) ether 4,4'-MDI: 4,4'-diphenylmethane diisocyanate TODI: 3,3'-dimethyl-4,4'-diisocyanatobiphenyl HER: resorcinol bis (2- (Hydroxyethyl) ether 1,4-butanediol Irganox 1010FF (CAS No. 6683-19-8) and 1098 (CAS No. 23128-74-7)

2. Polyurethane Synthesis 2.1 Polyurethanes based on HQEE, 4,4-MDI and PTHF (Comparative Example)
800.00 g of PolyTHF1000 was weighed into a 2 L tin can with 238.84 g of HQEE and briefly covered with nitrogen. The can was sealed with a suitable lid and heated to about 120 ° C. in a heating cabinet.

  The liquid components in the can were mixed on a lift with a propeller stirrer. Thereafter, 7.81 g of Irganox 1010FF and 7.81 g of Irganox 1098 were added and the mixture was stirred.

  The temperature of the mixture was carefully adjusted to 108 ° C. using a hot air gun. An addition of 505.1 g of 4,4'-MDI was made at 108C. MDI had a temperature of 45 ° C. Co-mixing was achieved using a propeller stirrer at 200 rpm. Upon reaching 110 ° C., the reaction mixture was poured into a Teflon dish. The Teflon dish was placed on a hot plate at 125 ° C.

  The solid slab was removed from the hot plate after 10 minutes and then heat treated in a heating cabinet at 80 ° C. for 24 hours. The cooled slab was ground with a cutting mill. The obtained granules were dried at 110 ° C. for 3 hours. Test specimens of 2 mm and 6 mm were produced by injection molding.

2.2 Polyurethane based on a mixture of HQEE and 1,4-butanediol (Example 1)
800.00 g of PolyTHF1000 was weighed into a 2 L tin can with 235.49 g of HQEE and 11.96 g of HER and 2.19 g of 1,4-butanediol and briefly covered with nitrogen. The can was sealed with a suitable lid and heated to about 120 ° C. in a heating cabinet.

  The liquid components in the can were mixed on a lift with a propeller stirrer. Thereafter, 7.81 g of Irganox 1010FF and 7.81 g of Irganox 1098 were added and the mixture was stirred.

  The temperature of the mixture was carefully adjusted to 108 ° C. using a hot air gun. An addition of 508.18 g of 4,4'-MDI was made at 108C. MDI had a temperature of 45 ° C. Co-mixing was achieved using a propeller stirrer at 200 rpm. Upon reaching 110 ° C., the reaction mixture was poured into a Teflon dish. The Teflon dish was placed on a hot plate at 125 ° C.

  The solid slab was removed from the hot plate after 10 minutes and then heat treated in a heating cabinet at 80 ° C. for 24 hours. The cooled slab was ground with a cutting mill. The obtained granules were dried at 110 ° C. for 3 hours. Test specimens of 2 mm and 6 mm were produced by injection molding.

2.3 Example 2
The preparation was carried out according to the same preparation method as described in connection with Example 1, except that 5% of 1,4-butanediol was used. The input materials are summarized in Table 1.

2.4 Example 3
The preparation was carried out according to the same preparation method as described in connection with Example 1, except that 10% 1,4-butanediol was used. The input materials are summarized in Table 1.

2.5 Polyurethane based on a mixture of HQEE and HER (Example 4)
800.00 g of PolyTHF1000 was weighed into a 2 L tin can with 227.18 g of HQEE and 11.96 g of HER and briefly covered with nitrogen. The can was sealed with a suitable lid and heated to about 120 ° C. in a heating cabinet.

  The liquid components in the can were mixed on a lift with a propeller stirrer. Thereafter, 7.81 g of Irganox 1010FF and 7.81 g of Irganox 1098 were added and the mixture was stirred.

  The temperature of the mixture was carefully adjusted to 108 ° C. using a hot air gun. An addition of 506.72 g of 4,4'-MDI was made at 108C. MDI had a temperature of 45 ° C. Co-mixing was achieved using a propeller stirrer at 200 rpm. Upon reaching 110 ° C., the reaction mixture was poured into a Teflon dish. The Teflon dish was placed on a hot plate at 125 ° C.

  The solid slab was removed from the hot plate after 10 minutes and then heat treated in a heating cabinet at 80 ° C. for 24 hours. The cooled slab was ground with a cutting mill. The obtained granules were dried at 110 ° C. for 3 hours. Test specimens of 2 mm and 6 mm were produced by injection molding.

2.6 Example 5
Manufacture was performed by the same manufacturing method described in connection with Example 4, except that 10% HER was used. The input materials are summarized in Table 1.

2.7 Example 6
The production was carried out according to the same production method as described in connection with Example 4, except that 50% HER was used. The input materials are summarized in Table 1.

2.8 Polyurethane based on a mixture of HQEE and PTHF (Example 7)
760.00 g of PolyTHF2000 and 40.00 g of PolyTHF650s were weighed into a 2 L tin with 268.52 g of HQEE and briefly covered with nitrogen. The can was sealed with a suitable lid and heated to about 120 ° C. in a heating cabinet.

  The liquid components in the can were mixed on a lift with a propeller stirrer. Thereafter, 7.68 g of Irganox 1010FF and 7.68 g of Irganox 1098 were added and the mixture was stirred.

  The temperature of the mixture was carefully adjusted to 108 ° C. using a hot air gun. Addition of 451.23 g of 4,4'-MDI was made at 108C. MDI had a temperature of 45 ° C. Co-mixing was achieved using a propeller stirrer at 200 rpm. Upon reaching 110 ° C., the reaction mixture was poured into a Teflon dish. The Teflon dish was placed on a hot plate at 125 ° C.

  The solid slab was removed from the hot plate after 10 minutes and then heat treated in a heating cabinet at 80 ° C. for 24 hours. The cooled slab was ground with a cutting mill. The obtained granules were dried at 110 ° C. for 3 hours. Test specimens of 2 mm and 6 mm were produced by injection molding.

2.9 Example 8
The production was carried out by the same production method as described in connection with Example 7, except that 10% of PolyTHF650s was used. The input materials are summarized in Table 1.

2.10 Example 9
The production was carried out by the same production method as described in connection with Example 7, except that 20% of PolyTHF650s was used. The input materials are summarized in Table 1.

2.11 Fluctuation of HQEE / HER ratio (Examples 10 to 18)
These examples were manufactured as in Example 1. The chain extender ratio was varied according to Table 2.

3. Mechanical properties 3.1 The measurements summarized in Tables 3a and 3b were obtained from extruded products of polyurethane obtained / from injection molded sheets.

  3.2 The measurements summarized in Tables 4a and 4b were obtained from injection molded sheet / extruded products of polyurethane obtained according to Examples 10-18.

3.3 The following properties of the resulting polyurethane were determined by the methods described.
Hardness: DIN ISO 7619-1
Tensile strength and elongation at break DIN 53504
Tear propagation resistance DIN ISO 34-1, B (b)
Wear measurement: DIN ISO 4649
Density: DIN EN ISO 1183-1, A
Compression strain DIN ISO 815

4 Extrusion Quality The image reproduced in FIG. 1 shows the extrusion quality, the described hard phase and the Shore hardness of 98 A of the different hoses of the TPU consisting of PTHF1000 produced in a pilot reaction extruder. The material obtained by manual casting had an equivalent appearance.

  A hose was manufactured from the materials of Comparative Example 1 and Example 5. The production of the hose was performed using a 45 mm single screw extruder manufactured by Arenz (3 zone screw, compression ratio 1: 2.5). The hose had dimensions of 8.2 mm x 5.8 mm.

  1 (a) and 1 (b) show a hose made from a thermoplastic polyurethane containing a HQEE-MDI hard phase (according to Comparative Example 1).

  1 (c) and 1 (d) show a hose made from a thermoplastic polyurethane containing a TPU with a HQEE / HER-MDI hard phase (according to Example 5).

  References

WO2006 / 082183A1 EP0922552A1 WO98 / 56845 WO2007 / 118827A1 EP0922552A1 WO2006 / 082183A1 WO2014 / 198779A1 WO2007 / 082838A1 WO94 / 20568A1

"Kunststoffhandbuch", volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1. "Kunststoffhandbuch", volume VII, edited by Viewweg and Hoechtlen, Carl Hanser Verlag, Munich, 1966 (pp. 103-113).

Claims (15)

At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time)
(Iii) at least one polyol composition;
A thermoplastic polyurethane obtainable or obtainable by the reaction of
A thermoplastic polyurethane, wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.   The thermoplastic polyurethane according to claim 1, wherein the chain extender (KV2) is selected from the group consisting of aliphatic and aromatic diols having a molecular weight of <500 g / mol.   The thermoplastic polyurethane according to claim 1 or 2, wherein the chain extender (KV1) of the general formula (I) is hydroquinone bis (2-hydroxyethyl) ether.   4. The thermoplastic polyurethane according to claim 1, wherein the at least one further chain extender (KV2) is selected from aliphatic and aromatic diols having a molecular weight of <350 g / mol. The at least one further chain extender (KV2) is a compound of general formula (II):

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 0, 1, 2, 3, 4, 5 or 6;
R3 _is selected from CH _3, CH 2 -CH ₃₎
The thermoplastic polyurethane according to any one of claims 1 to 3, which is:   The thermoplastic polyurethane according to any one of claims 1 to 5, wherein the polyol composition includes a polyol selected from the group consisting of polyetherol, polyesterol, polycaprolactone polyol, and polycarbonate polyol.   The thermoplastic according to any one of claims 1 to 6, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol. Polyurethane.   The polyol composition is a polyol (P1) selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1501 g / mol to 3000 g / mol, and a number average molecular weight Mn in the range of 500 g / mol to 1500 g / mol. The thermoplastic polyurethane according to any one of claims 1 to 7, comprising a polyol (P2) selected from the group consisting of polytetrahydrofuran having the following.   The polyisocyanate composition comprises 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TODI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PDI), 4,4′- 9. The composition according to claim 1, comprising an isocyanate selected from the group consisting of diphenylmethane diisocyanate (4,4′-MDI) and 2,4′-diphenylmethane diisocyanate (2,4′-MDI). 10. Thermoplastic polyurethane.   The polyisocyanate composition according to any one of claims 1 to 9, wherein the composition comprises a mixture of 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and 2,4'-diphenylmethane diisocyanate (2,4'-MDI). The thermoplastic polyurethane according to claim 1. At least components (i) to (iii):
(I) at least one polyisocyanate composition;
(Ii) at least one chain extender (KV1) of general formula (I),

(Where A is selected from O, N (R3), S, CH ₂ ,
Q is, O, N (R3), S, is selected from CH _2,
R1 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, is selected from OH,
R2 _{is, CH 2 - (CH 2)} n -OH, CH (CH 3) -CH 2 -OH, CH 2 -CH (CH 3) -OH, is selected from OH,
n is 1, 2, 3, 4, 5, 6;
R3 _is selected from CH _3, CH 2 -CH _3,
A and Q are not CH ₂ at the same time)
(Iii) at least one polyol composition;
A method for producing a thermoplastic polyurethane comprising the reaction of
A process wherein at least one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g / mol is used.   12. The thermoplastic polyurethane according to claim 1 or the process according to claim 11 for producing extruded products, films and moldings, in particular for producing cable coatings, hoses and seals. Use of a thermoplastic polyurethane obtainable or obtainable by means of:   13. The use according to claim 12, wherein the extruded product, the film or foil is reinforced with a filler.   A thermoplastic polyurethane according to any one of claims 1 to 10 or a method according to claim 11 for producing foamed films, foamed moldings or foamed particles and particle foams obtainable therefrom. Use of a thermoplastic polyurethane obtainable or obtainable by means of:   15. Use according to claim 14, wherein the foam film, foam molding or foam particles and the particle foam obtainable therefrom are reinforced with fillers.

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